CN105542155B - A kind of soluble azopolyamide liquid crystal material of normal-butyl substitution and preparation method thereof - Google Patents
A kind of soluble azopolyamide liquid crystal material of normal-butyl substitution and preparation method thereof Download PDFInfo
- Publication number
- CN105542155B CN105542155B CN201610035461.1A CN201610035461A CN105542155B CN 105542155 B CN105542155 B CN 105542155B CN 201610035461 A CN201610035461 A CN 201610035461A CN 105542155 B CN105542155 B CN 105542155B
- Authority
- CN
- China
- Prior art keywords
- azopolyamide
- normal
- liquid crystal
- soluble
- crystal material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to soluble azopolyamide liquid crystal material of a kind of normal-butyl substitution and preparation method thereof, belong to polymeric material field.The present invention is with 4,4' Azobenzene Diacyl Chlorides and aryl diamine are that raw material obtains azopolyamide by low temperature solution polymerization, reacted by NaH and DMSO, synthesize dimethyl sulfoxide (DMSO) carbanion, ion modification is carried out to polymer with this carbanion, polymer-modified ion and bromination of n-butane react to obtain the soluble azopolyamide of normal-butyl substitution, in side chain the introducing of normal-butyl improve the dissolubility of polymer in organic solvent.Synthesized normal-butyl substitution azopolyamide has good photochromic effect, and lysotropic liquid crystal can be produced in N, N dimethyl acetamides.The material will have great advantage and potentiality in terms of photochromic material, opto-mechanical controlled material, liquid crystal material and optics.
Description
Technical field
The present invention relates to soluble azopolyamide liquid crystal material of a kind of normal-butyl substitution and preparation method thereof, belongs to high
Molecular material field.
Background technology
Azobenzene can realize reversible cis-trans isomerization in the presence of light or heat, and therefore cause molecular dimension and idol
The change of polar moment, show the respondent behavior of reversible light and heat.Aromatic azo group is introduced into polymeric system, for hair
The feature for waving azo group serves strong impetus.Aromatic azo polymers can show liquid crystal liquid crystal property, non-linear
Optical and various response characteristics to light, suitable for manufacturing photochromic device, therefore show in image, optical information memory element, can
Changing the optical filtering of density, photographic template, light-operated switch etc. has significant application value.
Azo group occur under light illumination cis-trans isomerism transformation, this change procedure can cause main polymer chain curling and
Stretching, extension, significant photomechanical effect can be produced when the connection molecule for connecting azo group and main polymer chain is rigid radical.
Azopolyamide has the characteristics of high intensity, high-modulus.Exactly because but this feature, it is poor to result in its dissolubility, except
Can be dissolved in outside the concentrated sulfuric acid, be practically insoluble in other organic solvents, the cis-trans isomerism transformation of the azo group in molecular structure by
Resistance, photomechanical effect disappear.The free volume and dissolubility in organic solvent for improving azopolyamide are advantageous to molecule knot
The cis-trans isomerism transformation of azo group in structure.Document report is mainly using the structure of design modified aromatic race diamines at present, and 4,
The excellent azopolyamide of 4 '-azodibenzoyl chlorine synthesis performance, but the complicated synthesis technique of diamine monomer and expensive original
Material, limits the further research and application of this kind of azobenzene polymer.
Jaycox et al. [Polymer, 1998,39 (12):2589-2596；Polymer,1998,39(12):2597-
2605.] with the aromatic diamine of 4,4 '-azodibenzoyl chlorine and ketone group containing and ether at low temperature by polycondensation reaction,
A series of azopolyamides are synthesized.Due to the introducing of ehter bond and ketone group, polymer has in general polar organic solvent
Good dissolubility.The diamine monomer selected in such polymer synthesis process contains ketone group and ether structure simultaneously, synthesizes work
Skill is complicated, expensive raw material price, limits the further research and application of this kind of azobenzene polymer.Its polymer synthesized
Structure is as follows：
Zhu et al. [Polymer bulletin, 2008,61 (5):569-580.] with the 4,4'- bis- of trifluoromethyl substitution
Amino-diphenylethers reacts with azo acyl chlorides, has synthesized azopolyamide, and the introducing of trifluoromethyl is having azopolyamide
There is certain dissolubility in solvent, but 4, the 4'- diaminodiphenyl ethers preparation technology for the trifluoromethyl substitution selected is complicated, it is former
Expect expensive, limit further industrial applications etc..The structure of its polymer synthesized is as follows：
There is presently no finding that using 4,4'- azodibenzoyls chlorine and aryl diamine be raw material, obtained by polymerisation in solution
Azopolyamide, then on nitrogen-atoms in main chain hydrogen atom carry out substitution reaction, prepares N- normal-butyls substitution both with compared with
Big rigidity has the document report of good dissolubility azopolyamide in organic solvent simultaneously.This method is raw materials used inexpensive
Be easy to get, synthetic route is simple, in side chain the introducing of normal-butyl improve the dissolubility of polymer in organic solvent.Synthesized
Normal-butyl substitution azopolyamide there is good photochromic effect, molten cause liquid can be produced in DMA
It is brilliant.The material will have greatly in terms of as photochromic material, opto-mechanical controlled material, liquid crystal material and optics
Advantage and potentiality.
The content of the invention
The technical problems to be solved by the invention be overcome azopolyamide in organic solvent dissolubility difference the shortcomings that, carry
Azopolyamide material for a kind of substitution of normal-butyl and preparation method thereof.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of soluble azopolyamide of normal-butyl substitution
Liquid crystal material, there is following structural formula：
Wherein n is positive integer, and Ar is any of following four kinds of groups,
The present invention also provides a kind of preparation method of the soluble azopolyamide liquid crystal material of normal-butyl substitution, including such as
Lower step,
S1. the preparation of unsubstituted azopolyamide:Under ice-water bath and nitrogen protection, according to 1:2:120~200 mole
Ratio sequentially adds aryl diamine, anhydrous Lithium chloride and DMA into reaction vessel, and stirring is allowed to whole dissolvings,
Then it is the 4,4'- azos to add while stirring with the 4,4'- Azobenzene Diacyl Chlorides of aryl diamine equimolar amounts and molal quantity
The pyridine that 2-3 times of phthalyl chloride is measured, in -5~0 DEG C of more than sustained response 2h under the protection of nitrogen, make reaction product with water
Precipitation, wash, filter, use acetone extraction after filtration cakes torrefaction, dry unsubstituted azopolyamide, its reaction after the completion of extracting
Equation is such as shown in (I).
S2. the preparation of the soluble azopolyamide liquid crystal material of normal-butyl substitution：According to every 20-30mmol sodium hydrides pair
The ratio of 80-120mL anhydrous dimethyl sulfoxides is answered to add fluid dispersed sodium hydride and anhydrous dimethyl Asia into another reaction vessel
Sulfone, nitrogen are protected and are heated to 65-75 DEG C of dissolving 5min or until are produced without hydrogen；Add through it is dried just oneself
Alkane, after extraction with syringe remove mineral oil layer, repeat add n-hexane for several times until mineral oil it is completely cleared, obtain dimethyl
Sulfoxide carbanion solution, reaction equation is such as shown in (II)；Then to being added in the dimethyl sulfoxide (DMSO) carbanion solution
Molal quantity is the unsubstituted azopolyamide that the step S1 that 0.1-0.5 times of the sodium hydride is measured is obtained, and is stirred at 30-35 DEG C
Reaction is mixed to clarify completely to reaction solution, then it is the bromination of n-butane that 0.4-0.8 times of sodium hydride is measured to add molal quantity into reaction solution,
The stirring reaction 18-20h at 30-35 DEG C, add water to make to produce a large amount of floccule precipitations in reaction solution, filtered after standing a few hours,
Washing, dry, produce the soluble azopolyamide liquid crystal material of normal-butyl substitution, its course of reaction is such as shown in (III).
Specifically, the structural formula of the aryl diamine described in step S1 is H2N-Ar-NH2, wherein Ar is in following four kinds of groups
It is any,
I.e. aryl diamine is that aryl diamine is 4,4'- diaminodiphenyl ethers, p-phenylenediamine, 4,4'- MDAs and 4,
Any of 4'- diaminodiphenylsulfones.
Specifically, the mol ratio of aryl diamine, anhydrous Lithium chloride and DMA is most preferably 1 in step S1:
2:161.2。
Specifically, the molal quantity of the pyridine described in step S1 is 2 times of 4,4'- Azobenzene Diacyl Chlorides.
Specifically, the usage ratio of the sodium hydride and anhydrous dimethyl sulphoxide described in step S2 is most preferably per 25mmol hydrogen
Change sodium and correspondingly use 100mL anhydrous dimethyl sulphoxides.
Specifically, the weight content of sodium hydride is 50%-60% in fluid dispersed sodium hydride described in step S2.
Specifically, the fluid dispersed sodium hydride described in step S2 is proportionally added into reaction with anhydrous dimethyl sulphoxide and held
After device, under nitrogen protection, using oil bath heating to 70 DEG C and maintain the temperature until without hydrogen produce.
Specifically, mole of the unsubstituted azopolyamide added in step S2 in dimethyl sulfoxide (DMSO) carbanion solution
Number is 0.2 times of the sodium hydride.
Specifically, the drying described in step S1 and S2 be in vacuum drying oven dry and drying time be no less than 24h.
It is interpreted as the meter to azo polyamide slices section when azopolyamide in the present invention is with its dosage of molal unit meter
Amount, the distribution without being limited to azopolyamide molecular weight have monodispersity.
By introducing side chain normal-butyl in azopolyamide molecular structure, it will be apparent that improve polymer in organic solvent
In dissolubility, preparation technology is simple, and raw material is cheap and easy to get, mild condition, and high income is easy to implement, and solvent is through distillation purifying
After can be recycled, change conventional method and improve azopolyamide dissolubility defect (conventional method is to improve diamine and two
Expensive raw material is modified and used to first acyl chlorides labyrinth).In addition, the introducing of normal-butyl, improves the film forming of polymer, increases
The machinability of polyamide, it ensure that being smoothed out for azo group isomerization.Therefore the material as photochromic material,
To there are great advantage and potentiality in terms of opto-mechanical controlled material, liquid crystal material and optics.
Brief description of the drawings
Fig. 1 is the soluble azopolyamide hydrogen nuclear magnetic resonance spectrogram of normal-butyl substitution prepared by the embodiment of the present invention 1；
Fig. 2 is the ultraviolet suction of the soluble azopolyamide liquid crystal material of normal-butyl substitution prepared by the embodiment of the present invention 1
Receive spectrum；
Fig. 3 is that the solution of the soluble azopolyamide liquid crystal material of normal-butyl substitution prepared by the embodiment of the present invention 1 exists
The liquid crystal figure observed under petrographic microscope；
Fig. 4 is the liquid of the solution of soluble azopolyamide liquid crystal material after increase microscope multiplying power on the basis of Fig. 3
Crystalline substance figure.
Embodiment
Below by specific embodiment and with reference to accompanying drawing, the invention will be further described, and following examples are descriptive
, it is not limited, it is impossible to once limit protection scope of the present invention.
Method used in the present invention, it is conventional method unless otherwise required, reagent used in the present invention, such as
It is commercially available prod without particular provisions.
Embodiment 1
A kind of preparation of the soluble azopolyamide liquid crystal material of normal-butyl substitution：
S1. equipped with agitator, in the three-necked bottle of ice-water bath and nitrogen inlet-outlet, the 4,4'- of 3.0mmol is sequentially added
Diaminodiphenyl ether, 6.0mmol anhydrous Lithium chlorides, 15mL (161.2mmol) DMA (DMAc), stirring is allowed to
All dissolvings, 3mmol 4,4'- Azobenzene Diacyl Chlorides and 6mmol pyridines are then added while stirring, under the protection of nitrogen
Reaction system viscosity is significantly increased after -5-0 DEG C of reactions, 15min, and after reacting 2h, reaction product is settled out in 500ml water
Come, wash, filter, 120 DEG C of vacuum drying 24h, with acetone extraction 24h, 80 DEG C of vacuum drying 24h, it is unsubstituted to obtain yellow
Azopolyamide.
S2. to equipped with thermometer, agitator, condenser, nitrogen ingress pipe, barrier film tri- mouthfuls of reaction flasks of 500mL in, add
Enter 100mL anhydrous dimethyl sulfoxides (DMSO) and 25mmol sodium hydrides (the fluid dispersed sodium hydride of hydrogenation sodium content 60%),
70 DEG C of dissolving 5min of the lower oil bath heating of nitrogen protection or until produced without hydrogen, add through dried n-hexane, together
When with syringe remove mineral oil layer.Repeat add n-hexane for several times until mineral oil it is completely cleared, the dimethyl sulfoxide (DMSO) of generation
Carbanion solution is the liquid of low viscosity, yellow green, then adds in S1 the unsubstituted azos of 5mmol being dried in vacuo and gathers
Acid amides, and stirring reaction about 3h clarifies to complete at 35 DEG C, then 10mmol bromination of n-butane is added into reaction solution, at 35 DEG C
Stirring reaction 18h, 500mL deionized waters are added into product, produce a large amount of floccule precipitations, filtered after standing a few hours,
Vacuum drying 24h under the conditions of 60 DEG C, products therefrom are the soluble azopolyamide material of normal-butyl substitution.
Embodiment 2
A kind of preparation of the soluble azopolyamide liquid crystal material of normal-butyl substitution：
S1. equipped with agitator, in the three-necked bottle of ice-water bath and nitrogen inlet-outlet, sequentially add 3.0mmol to benzene
Diamines, 6.0mmol anhydrous Lithium chlorides, 18.6mL (200mmol) DMA (DMAc), stirring are allowed to all molten
Solution, 3mmol 4,4'- Azobenzene Diacyl Chlorides and 6mmol pyridines is then added while stirring, in -5-0 under the protection of nitrogen
DEG C reaction, reaction system viscosity is significantly increased after 15min, and after reacting 2h, reaction product is precipitated out in 500ml water, washing,
Filter, 120 DEG C of vacuum drying 24h, with acetone extraction 24h, 80 DEG C of vacuum drying 24h, obtain the unsubstituted azo polyamides of yellow
Amine.
S2. to equipped with thermometer, agitator, condenser, nitrogen ingress pipe, barrier film tri- mouthfuls of reaction flasks of 500mL in, add
Enter 80mL anhydrous dimethyl sulfoxides (DMSO) and 20mmol sodium hydrides (the fluid dispersed sodium hydride of hydrogenation sodium content 50%), in nitrogen
75 DEG C of oil bath heating dissolving 5min or until produced without hydrogen under gas shielded, add through dried n-hexane, simultaneously
Mineral oil layer is removed with syringe.Repeat add n-hexane for several times until mineral oil it is completely cleared, the dimethyl sulfoxide (DMSO) carbon of generation
Negative solution is the liquid of low viscosity, yellow green, then adds in S1 the unsubstituted azo polyamides of 4mmol being dried in vacuo
Amine, and stirring reaction about 3h clarifies to complete at 30 DEG C, then 12mmol bromination of n-butane is added into reaction solution, stirred at 35 DEG C
Reaction 20h is mixed, 500mL deionized waters are added into product, a large amount of floccule precipitations is produced, is filtered after standing a few hours, 60
Vacuum drying 24h under the conditions of DEG C, products therefrom are the soluble azopolyamide material of normal-butyl substitution.
Embodiment 3
A kind of preparation of the soluble azopolyamide liquid crystal material of normal-butyl substitution：
S1. equipped with agitator, in the three-necked bottle of ice-water bath and nitrogen inlet-outlet, the 4,4'- of 3.0mmol is sequentially added
MDA, 6.0mmol anhydrous Lithium chlorides, 11.2mL (120mmol) DMA (DMAc), stirring makes
Whole dissolving, then while stirring add 3mmol 4,4'- Azobenzene Diacyl Chlorides and 8mmol pyridines, in the protection of nitrogen
Under in -5-0 DEG C of reactions, reaction system viscosity is significantly increased after 15min, and after reacting 2h, reaction product is settled out in 500ml water
Come, wash, filter, 120 DEG C of vacuum drying 24h, with acetone extraction 24h, 80 DEG C of vacuum drying 24h, it is unsubstituted to obtain yellow
Azopolyamide.
S2. to equipped with thermometer, agitator, condenser, nitrogen ingress pipe, barrier film tri- mouthfuls of reaction flasks of 500mL in, add
Enter 100mL anhydrous dimethyl sulfoxides (DMSO) and 30mmol sodium hydrides (the fluid dispersed sodium hydride of hydrogenation sodium content 60%),
65 DEG C of dissolving 5min of the lower oil bath heating of nitrogen protection or until produced without hydrogen, add through dried n-hexane, together
When with syringe remove mineral oil layer.Repeat add n-hexane for several times until mineral oil it is completely cleared, the dimethyl sulfoxide (DMSO) of generation
Carbanion solution is the liquid of low viscosity, yellow green, then adds in S1 the unsubstituted azos of 3mmol being dried in vacuo and gathers
Acid amides, and stirring reaction about 3h clarifies to complete at 30 DEG C, then 18mmol bromination of n-butane is added into reaction solution, at 30 DEG C
Stirring reaction 20h, 500mL deionized waters are added into product, produce a large amount of floccule precipitations, filtered after standing a few hours,
Vacuum drying 24h under the conditions of 60 DEG C, products therefrom are the soluble azopolyamide material of normal-butyl substitution.
Embodiment 4
A kind of preparation of the soluble azopolyamide liquid crystal material of normal-butyl substitution：
S1. equipped with agitator, in the three-necked bottle of ice-water bath and nitrogen inlet-outlet, sequentially add
3.0mmol 4,4'- diaminodiphenylsulfones, 6.0mmol anhydrous Lithium chlorides, 15mL (161.2mmol) N, N- diformazan
Yl acetamide (DMAc), stirring be allowed to whole dissolvings, then while stirring add 3mmol 4,4'- Azobenzene Diacyl Chlorides and
9mmol pyridines, reaction system viscosity significantly increases after -5-0 DEG C of reactions, 15min under the protection of nitrogen, after reacting 2h, instead
Answer product to be precipitated out in 500ml water, wash, filter, 120 DEG C of vacuum drying 24h, with acetone extraction 24h, 80 DEG C of vacuum are done
Dry 24h, obtain the unsubstituted azopolyamide of yellow.
S2. to equipped with thermometer, agitator, condenser, nitrogen ingress pipe, barrier film tri- mouthfuls of reaction flasks of 500mL in, add
Enter 100mL anhydrous dimethyl sulfoxides (DMSO) and 20mmol sodium hydrides (the fluid dispersed sodium hydride of hydrogenation sodium content 60%),
70 DEG C of dissolving 5min of the lower oil bath heating of nitrogen protection or until produced without hydrogen, add through dried n-hexane, together
When with syringe remove mineral oil layer.Repeat add n-hexane for several times until mineral oil it is completely cleared, the dimethyl sulfoxide (DMSO) of generation
Carbanion solution is the liquid of low viscosity, yellow green, then adds in S1 the unsubstituted azos of 10mmol being dried in vacuo
Polyamide, and stirring reaction about 3h clarifies to complete at 30 DEG C, then 16mmol bromination of n-butane is added into reaction solution, 30 DEG C
Lower stirring reaction 20h, 500mL deionized waters are added into product, produce a large amount of floccule precipitations, filtered after standing a few hours,
The vacuum drying 24h under the conditions of 60 DEG C, products therefrom are the soluble azopolyamide material of normal-butyl substitution.
Test case
By taking the soluble azopolyamide liquid crystal material of the normal-butyl substitution prepared in embodiment 1 as an example, its dissolving is tested
Property, nuclear magnetic resonance map, photochromic properties and liquid crystal behavior.The soluble azopolyamide liquid crystal that normal-butyl is substituted below
Material is referred to as polymer.
Nuclear magnetic resonance map such as Fig. 1 of the soluble azopolyamide liquid crystal material of normal-butyl substitution prepared by embodiment 1
It is shown：δ=10.50ppm is the connected hydrogen atom of nitrogen-atoms, and δ=0.978-4.335ppm is hydrogen chemical shifts on normal-butyl, is not taken
For azopolyamide, proton nmr spectra does not have 0.978-4.335ppm presence, it was demonstrated that there occurs the substitution of N- normal-butyls for polymer
Reaction.
The solubility property test of polymer：The soluble azopolyamide liquid crystal material that 0.05g normal-butyl is substituted is complete
Complete immersion is placed a week at room temperature in 1mL solvent to be measured, observes dissolving situation, and test result see the table below：
Note：+++ it is readily soluble；++ dissolving；+ slightly soluble；- insoluble.
As seen from the above table：Substituted by side chain normal-butyl, the dissolubility of polymer in organic solvent substantially increases.Molecule
Structure introduces side chain normal-butyl, distorts strand, and the arrangement of strand tends to be random, intermolecular gap increase, strand
Accumulation it is loose, polymer is not easy to crystallize, and strand easily rotates freely, and increases the free volume of intramolecular, reduces polymerization
The active force of thing molecule interchain, solvent molecule are easily accessible in polymer, so as to improve the solubility property of polymer.
The photochromic properties test of polymer：Normal-butyl azopolyamide is dissolved in DMAc solvents, with it is ultraviolet can
See that spectrophotometer measures UV absorption, then solution is carried out to the ultraviolet light of different time, further tested
UV absorption.
The absorbance at maximum wavelength that can be seen that the strong peak of illumination post-consumer polymer from Fig. 2 ultraviolet absorpting spectrum subtracts rapidly
It is small.Polymer solution illumination to the time of stable state is 30min, and the polymer solution exists reaching equilibrium state, absorption curve
Occur flex point (extinction point) at 294nm, will not occur new absworption peak again afterwards.This shows that polymer is cis there occurs trans one
Light isomery changes, and the side reactions such as photo-crosslinking do not occur.It also found in test process, by polymer after illumination restoration to equilibrium state
After solution avoid light place 70h, the ultraviolet absorption curve of the material is returned to no light condition again.
Polymer lyotropic liquid crystal method of testing is：The sample of prepared polymer is dissolved in a certain amount of DMAc, is applied to
On slide, covered, observed on polarization microscope using crossed polarized light.
Understand that polymer solution has obvious texture by Fig. 3 and Fig. 4 lysotropic liquid crystal displaing micro picture, present obvious
Optical anisotropy.When the concentration of polymer reaches a certain certain concentration, spy can be presented in the polymer under polarization microscope
Fixed texture.This is due to the rigidity knot in polymer chain when lyotropic liquid crystal polymers solution concentration reaches its critical concentration
Structure groups density has reached a suitable degree.Under this density, the polymer rigid building stone distance foot in solution
It is enough near, hydrogen bond is easily formed, intermolecular hydrogen bond force makes the rigid structure group in polymer molecule according to certain regular row
The orientation of row formation rule, so as to produce lysotropic liquid crystal state, optically anisotropic texture can be observed under petrographic microscope.
In summary, the present invention is prepared for the soluble azopolyamide liquid crystal material of normal-butyl substitution, and it is organic
There is good dissolubility in solvent, it is a kind of photochromic material, and a kind of liquid crystal material.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (9)
1. a kind of preparation method of the soluble azopolyamide liquid crystal material of normal-butyl substitution, it is characterised in that including as follows
Step,
S1. the preparation of unsubstituted azopolyamide:Under ice-water bath and nitrogen protection, according to 1:2:120~200 molar ratio
Aryl diamine, anhydrous Lithium chloride and DMA are sequentially added into reaction vessel, stirring is allowed to whole dissolvings, then
It is the 4,4'- azobenzenes two to add while stirring with the 4,4'- Azobenzene Diacyl Chlorides of aryl diamine equimolar amounts and molal quantity
The pyridine that 2-3 times of formyl chloride is measured, in -5~0 DEG C of more than sustained response 2h under the protection of nitrogen, precipitate reaction product with water,
Washing, is filtered, and uses acetone extraction after filtration cakes torrefaction, dry unsubstituted azopolyamide, its reactional equation after the completion of extracting
Formula is such as shown in (I)；
S2. the preparation of the soluble azopolyamide liquid crystal material of normal-butyl substitution：It is corresponding according to every 20-30mmol sodium hydrides
The ratio of 80-120mL anhydrous dimethyl sulfoxides adds fluid dispersed sodium hydride and anhydrous dimethyl sulfoxide into another reaction vessel,
Nitrogen is protected and is heated to 65-75 DEG C of dissolving 5min or until is produced without hydrogen；Add through dried n-hexane, extraction
After taking with syringe remove mineral oil layer, repeat add n-hexane for several times until mineral oil it is completely cleared, obtain dimethyl sulfoxide (DMSO)
Carbanion solution, reaction equation is such as shown in (II)；Then to addition mole in the dimethyl sulfoxide (DMSO) carbanion solution
The unsubstituted azopolyamide that number obtains for the step S1 that 0.1-0.5 times of the sodium hydride is measured, and stirred instead at 30-35 DEG C
It should be clarified completely to reaction solution, then it is the bromination of n-butane that 0.4-0.8 times of sodium hydride is measured to add molal quantity into reaction solution,
Stirring reaction 18-20h at 30-35 DEG C, add water to make to produce a large amount of floccule precipitations in reaction solution, filter, wash after standing a few hours
Wash, dry, produce the soluble azopolyamide liquid crystal material of normal-butyl substitution, its course of reaction is such as shown in (III)；
2. a kind of preparation method of the soluble azopolyamide liquid crystal material of normal-butyl substitution according to claim 1,
Characterized in that, the structural formula of the aryl diamine described in step S1 is H2N-Ar-NH2, wherein Ar is appointing in following four kinds of groups
One kind,
3. a kind of preparation method of the soluble azopolyamide liquid crystal material of normal-butyl substitution according to claim 1,
Characterized in that, the mol ratio of aryl diamine, anhydrous Lithium chloride and DMA is 1 in step S1:2:161.2.
4. a kind of preparation method of the soluble azopolyamide liquid crystal material of normal-butyl substitution according to claim 1,
Characterized in that, the molal quantity of the pyridine described in step S1 is 2 times of 4,4'- Azobenzene Diacyl Chlorides.
5. a kind of preparation method of the soluble azopolyamide liquid crystal material of normal-butyl substitution according to claim 1,
Characterized in that, the sodium hydride described in step S2 is corresponding per 25mmol sodium hydrides with the usage ratio of anhydrous dimethyl sulphoxide
Use 100mL anhydrous dimethyl sulphoxides.
6. a kind of preparation method of the soluble azopolyamide liquid crystal material of normal-butyl substitution according to claim 1,
Characterized in that, the weight content of sodium hydride is 50%-60% in fluid dispersed sodium hydride described in step S2.
7. a kind of preparation method of the soluble azopolyamide liquid crystal material of normal-butyl substitution according to claim 1,
Characterized in that, the fluid dispersed sodium hydride described in step S2 is proportionally added into reaction vessel with anhydrous dimethyl sulphoxide
Afterwards, under nitrogen protection, using oil bath heating to 70 DEG C and maintain the temperature until without hydrogen produce.
8. a kind of soluble azopolyamide liquid crystal material of normal-butyl substitution according to any one of claim 1 to 7
Preparation method, it is characterised in that the unsubstituted azopolyamide added in step S2 in dimethyl sulfoxide (DMSO) carbanion solution
Molal quantity be 0.2 times of the sodium hydride.
9. a kind of soluble azopolyamide liquid crystal material of normal-butyl substitution according to any one of claim 1 to 7
Preparation method, it is characterised in that the drying described in step S1 and S2 be in vacuum drying oven dry and drying time it is many
In 24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610035461.1A CN105542155B (en) | 2016-01-19 | 2016-01-19 | A kind of soluble azopolyamide liquid crystal material of normal-butyl substitution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610035461.1A CN105542155B (en) | 2016-01-19 | 2016-01-19 | A kind of soluble azopolyamide liquid crystal material of normal-butyl substitution and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105542155A CN105542155A (en) | 2016-05-04 |
| CN105542155B true CN105542155B (en) | 2017-12-19 |
Family
ID=55821740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610035461.1A Expired - Fee Related CN105542155B (en) | 2016-01-19 | 2016-01-19 | A kind of soluble azopolyamide liquid crystal material of normal-butyl substitution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105542155B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343242A (en) * | 2019-07-04 | 2019-10-18 | 岭南师范学院 | Photochromic hyperbranched azopolyamide of one kind and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254441A (en) * | 2012-09-11 | 2013-08-21 | 苏州大学 | Preparation method of comb type copolymer containing polyamide chain segments |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090214968A1 (en) * | 2008-02-27 | 2009-08-27 | Konica Minolta Business Technologies, Inc. | Mixture of bisamine compounds, electrophotographic photoreceptor, method for forming image, and image forming apparatus |
-
2016
- 2016-01-19 CN CN201610035461.1A patent/CN105542155B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254441A (en) * | 2012-09-11 | 2013-08-21 | 苏州大学 | Preparation method of comb type copolymer containing polyamide chain segments |
Non-Patent Citations (2)
| Title |
|---|
| "主链型偶氮苯改性聚芳酰胺的合成及表征";尤艳姣等;《化工新型材料》;20070731;第35卷(第7期);第33-34及45页 * |
| "新型芳香聚酰胺及磺化芳香聚酰胺的研究";赵晶;《中国优秀硕士学位论文全文数据库》;20120715;第工程科技I辑卷(第7期);第B016-198页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105542155A (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102911359B (en) | Transparent polyimide and preparation method thereof | |
| CN109796590A (en) | A kind of polyimide resin and transparent polyimide film | |
| CN102675637B (en) | Electrochromatic polyimide and preparation method thereof | |
| CN101717648A (en) | Soluble polyimide liquid crystal vertical alignment agent, prepration method and liquid crystal box prepared thereby | |
| Wu et al. | Ratiometric and colorimetric sensors for highly sensitive detection of water in organic solvents based on hydroxyl-containing polyimide-fluoride complexes | |
| CN104119532A (en) | Transparent polyimide resin and preparation method thereof | |
| US20090041955A1 (en) | Alignment material for liquid crystal display device of vertical alignment mode and method of preparing the same | |
| Wu et al. | Multifunctional polyimides by direct silyl ether reaction of pendant hydroxy groups: Toward low dielectric constant, high optical transparency and fluorescence | |
| CN113480442A (en) | Cross-linkable diamine monomer, preparation method and application thereof in preparation of polyimide | |
| CN105542155B (en) | A kind of soluble azopolyamide liquid crystal material of normal-butyl substitution and preparation method thereof | |
| Mallakpour et al. | Synthesis and properties of novel soluble aromatic polyamides derived from 5-(2-phthalimidyl-3-methyl butanoylamino) isophthalic acid and aromatic diamines | |
| Wei et al. | Synthesis, characterization, and photo‐responsive properties of Y‐shaped amphiphilic azo triblock copolymer | |
| CN108929243B (en) | Diamine monomer containing asymmetric fluorophore structure and preparation method and application thereof | |
| JP6740527B2 (en) | Polymers, optical materials and lenses | |
| CN106832278A (en) | One class high transparency copoly type fluorine-containing polyimide film material and preparation method thereof | |
| CN102167826A (en) | Optically active polyamide imide and preparation method as well as application thereof | |
| Wang et al. | Tunable Cis-cisoid Helical Conformation of Poly (3, 5-disubstibuted phenylacetylene) s Stabilized by n→ π* Interaction | |
| Amer et al. | Liquid‐crystalline azobenzene‐containing ferrocene‐based polymers: study on synthesis and properties of main‐chain ferrocene‐based polyesters with azobenzene in the side chain | |
| Xia et al. | The effect of phthalimide side chains on the thermal stability and rubbing resistance of polyimide used as a liquid crystal vertical alignment layer | |
| CN106496557A (en) | A kind of preparation method of high transparency high temperature resistant fluorinated polyimide resin | |
| Sogawa et al. | α‐Propargyl amino acid‐derived optically active novel substituted polyacetylenes: Synthesis, secondary structures, and responsiveness to ions | |
| CN107903417B (en) | Preparation and application of quinoxaline group bridged side chain type sulfonated polyimide | |
| CN104119531A (en) | Diffluent transparent polyimide resin and preparation method thereof | |
| CN105754097B (en) | A kind of clear polyimides resin and preparation method thereof | |
| CN106046363B (en) | One kind is containing fluorene structured high dissolubility Nomex of tetramethoxy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171219 Termination date: 20210119 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |